The first solvent-free cyclotrimerization reaction of arylethynes catalyzed by rhodium porphyrins

Different rhodium(III) porphyrin chlorides have been used as catalysts for the cyclotrimerization of several arylethynes, giving in many cases high yields in substituted benzenes and selectivities based on the steric hindrance of the macrocycles and on the substitution of the substrates

A sustainable two-phase procedure for V-catalyzed toluene oxidative bromination with H2O2–KBr

A sustainable V(V) and Mo(VI) catalysed two-phase procedure for bromination of toluene under quite mild conditions is proposed; H2O2 is the primary oxidant and KBr is the bromine source; metal precursors are commercially available salts. The reaction is efficient without any additional solvent. By using PhCH3 as a solvent/substrate good yields, together with interesting selectivity toward the formation of PhCH2Br, are obtained with both metal ions. Recycling of the catalytic phase is also possible. Useful information on the V-peroxido chemistry was obtained

Tailored functionalization of natural phenols to improve biological activity

Phenols are widespread in nature, being the major components of several plants and essential oils. Natural phenols' anti-microbial, anti-bacterial, anti-oxidant, pharmacological and nutritional properties are, nowadays, well established. Hence, given their peculiar biological role, numerous studies are currently ongoing to overcome their limitations, as well as to enhance their activity. In this review, the functionalization of selected natural phenols is critically examined, mainly highlighting their improved bioactivity after the proper chemical transformations. In particular, functionalization of the most abundant naturally occurring monophenols, diphenols, lipidic phenols, phenolic acids, polyphenols and curcumin derivatives is explored

Salophen and salen oxo vanadium complexes as catalysts of sulfides oxidation with H 2O 2: Mechanistic insights

The application of V(V) catalysts in oxidation of sulfides with peroxides offers an efficient procedure, that is compatible with different functional groups, and leads to good yields and selectivities. However, the understanding of the factors affecting the reactivity of different catalysts is still far to be complete. An experimental and theoretical study on a series of V(V) complexes containing variously substituted salen and salophen ligands is reported with the aim to correlate the activity of the catalysts with the electronic character of the vanadium center. The results obtained indicate that steric factors play a major role in determining the outcome of the reaction, often overcoming the electronic effects. Theoretical results suggest the intervention in the catalytic cycle of an hydroperoxo vanadium species

Investigation of VO-salophen complexes electronic structure

Vanadyl N,N'-bis(salicylidene)-o-phenylenediamine (salophen) complexes have been extensively investigated by cyclic voltammetry, UV-visible spectroscopy and theoretical calculations in MeCN, THF (tetrahydrofuran) and DMF (N,N-dimethylformamide), in order to elucidate the overall factors that influence the electronic density of the metal and therefore the properties of these complexes in various applications. Different substituents were introduced into the salophen skeleton to change the vanadium electron density. Results obtained and here presented showed that the substituents influence the metal electronic character in a way that cannot be easily predicted by considering only the electronic effect. Similarly, the solvent polarity or coordination ability affects the metal complex properties in an unpredictable way. Therefore, experimental and theoretical data here collected are a powerful tool to a priori design salophen ligands to obtain vanadyl complexes having the specific electronic properties suitable for desired applications

A stoichiometric solvent-free protocol for acetylation reactions

Considering the remarkable relevance of acetylated derivatives of phenols, alcohols, and aryl and alkyl thiols in different areas of biology, as well as in synthetic organic chemistry, a sustainable solvent-free approach to perform acetylation reactions is proposed here. Acetylation reactions are classically performed using excess of acetic anhydride (Ac2O) in solvent-free conditions or by eventually working with stoichiometric amounts of Ac2O in organic solvents; both methods require the addition of basic or acid catalysts to promote the esterification. Therefore, they usually lead to the generation of high amounts of wastes, which sensibly raise the E-factor of the process. With the aim to develop a more sustainable system, a solvent-free, stoichiometric acetylation protocol is, thus, proposed. The naturally occurring phenol, thymol, can be converted to the corresponding-biologically active-ester with good yields, in the presence of 1% of VOSO4. Interestingly, the process can be efficiently adopted to synthesize other thymyl esters, as well as to perform acetylation of alcohols and aryl and alkyl thiols. Remarkably, a further improvement has been achieved replacing Ac2O with its greener alternative, isopropenyl acetate (IPA)

Finding the Center of Mass of a Soft Spring

This article shows how to use calculus to find the center of mass position of a soft cylindrical helical spring that is suspended vertically. The spring is non-uniformly stretched by the action of gravity. A general expression for the vertical position of the center of mass is obtained.Comment: LaTeX, 7 pages, 2 figures. Minor changes to agree with published versio

Ionic Liquids as Reaction Media in Catalytic Oxidations with Manganese and Iron Pyridyl Triazacyclononane Complexes

A family of bioinspired iron and manganese complexes of general formula [MII(CF3SO3)2(Me,XPyTACN)], where Me,XPyTACN = 1-[2’-(6-X-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, and M = Fe, and Mn has been studied as efficient catalytic systems for hydrogen peroxide oxidation reactions. Previous work revealed that the manganese derivative [MnII(CF3SO3)2(Me,HPyTACN)], 1, in acetonitrile exhibits a high catalytic activity in the epoxidation of a wide range of olefins (TON: 810-4500), using acetic acid and hydrogen peroxide as primary oxidant. The analogous iron based complex [FeII(CF3SO3)2(Me,HPyTACN)], 2a and [FeII(CF3SO3)2(Me,MePyTACN)], 2b promote the high added value oxidation reaction of alkanes in mild conditions. In this work sustainability and selectivity of the oxidative system is improved with the use of the ionic liquids (ILs) as reaction medium. The possibility to recycle the catalytic phase without loss of the activity with respect to the original reaction in acetonitrile (MeCN) is reported

Unveiling KuQuinone redox species: an electrochemical and computational cross study

The study of the electrochemical properties of variegated quinones is a fascinating topic in chemistry. In fact, redox reactions occurring with quinoid scaffolds are essential for most of their applications in biological systems, in photoelectrochemical devices, and in many other fields. In this paper, a detailed investigation of KuQuinones' redox behavior is presented. The distinctiveness of such molecules is the presence in the structure of two condensed naphthoquinone units, which implies the possibility to undergo multiple one-electron reduction processes. Solvent, supporting electrolyte, and hydrogen bond donor species effects have been elucidated. Changing the experimental parameters provoked significant shift of the redox potential for each reduction process. In particular, additions of 2,2,2-trifluoroethanol as a hydrogen bond donor in solution as well as Lewis acid coordination were crucial to obtain important shifts of the redox potentials toward more favorable values. UV-vis-NIR spectroelectrochemical experiments and DFT calculations are also presented to clarify the nature of the reduced species in solution